EP1984306B1 - Colored glass compositions - Google Patents

Colored glass compositions Download PDF

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Publication number
EP1984306B1
EP1984306B1 EP07716289.9A EP07716289A EP1984306B1 EP 1984306 B1 EP1984306 B1 EP 1984306B1 EP 07716289 A EP07716289 A EP 07716289A EP 1984306 B1 EP1984306 B1 EP 1984306B1
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EP
European Patent Office
Prior art keywords
weight percent
ppm
glass composition
glass
present
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EP07716289.9A
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German (de)
French (fr)
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EP1984306A1 (en
Inventor
Dennis G. Smith
Larry J. Shelestak
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Vitro SAB de CV
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Vitro SAB de CV
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Priority to PL07716289T priority Critical patent/PL1984306T3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/02—Compositions for glass with special properties for coloured glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass

Definitions

  • the present invention relates to glass compositions, particularly, glass compositions that include minimal amounts of colorants and other property modifying materials but exhibit intense colors.
  • Glass substrates are used in a variety of applications such as automotive applications, architectural applications, aerospace applications, etc. Glass substrates are also used in furniture (i.e., table tops, shelving, etc.) and appliances. Depending on the end use of the glass substrate, it is desirable for the glass substrate to exhibit certain. (a) aesthetic properties, such as, but not limited to, color and (b) solar control properties, such as, but not limited to, total solar energy transmittance ("TSET”), visible light transmittance (Lta), etc.
  • TSET total solar energy transmittance
  • Lta visible light transmittance
  • the aesthetic properties and solar control properties of a glass substrate can be modified in several of different ways.
  • a first way involves depositing a coating on the surface of a glass substrate.
  • a second way involves changing the chemical composition (i.e., the type of materials that make up the glass composition and/or the weight percentages of the various materials in the glass composition) that make up the glass substrate.
  • colorants and/or other materials capable of modifying the solar properties of the glass composition are added to a well known base glass composition, such as a soda-lime-silica base glass composition, to provide a glass substrate capable of exhibiting unique performance properties.
  • the effect of one colorant or one material capable of modifying the solar properties of the glass composition may be known (for example, it is known that adding FeO to a base glass composition increases the infrared (IR) absorption of the glass composition), it is the essence of invention to use various colorants and/or materials capable of modifying the solar properties of the glass composition, each colorant or material capable of producing a unique effect individually, to achieve a combination of properties collectively.
  • IR infrared
  • EP 1 201 615 teaches colored glasses with high transmission.
  • specific materials capable of modifying the aesthetic and/or solar properties of a glass composition are added in specific amounts to a soda-lime-silica base glass composition to provide colored glass substrates.
  • the glass substrates of the present invention can be exhibit various colors such as, but not limited to, blue, green, yellow, bronze and gray.
  • the glass substrates of the present invention can also exhibit an Lta of equal to or greater than 80% which is generally desirable for glass substrates used in furniture and appliances.
  • the present invention is a glass composition
  • a glass composition comprising a base glass composition comprising: SiO 2 from 65 to 75 weight percent, Na 2 O from 10 to 20 weight percent, CaO from 5 to 15 weight percent, MgO from 0 to 5 weight percent, Al 2 O 3 from 0 to 5 weight percent, K 2 O from 0 to 5 weight percent, and BaO from 0 to 1 weight percent, and a colorant and property modifying portion comprising: total iron up to 0.02 weight percent, CeO 2 from 0.05 to 1.5 weight percent, CoO up to 50PPM, Se up to 15 PPM, Cr 2 O 3 up to 500 PPM, CuO up to 0.5 weight percent, V 2 O 5 up to 0.3 weight percent, TiO 2 up to 1 weight percent, NiO up to 200 PPM, Er 2 O 3 up to 3 weight percent, MnO 2 up to 0.6 weight percent, and Nd 2 O 3 up to 2 weight percent, wherein the glass composition has a redox ratio up to 0,55 and comprises at least one of Er 2 O 3 from 0,
  • the present invention is a glass sheet comprising a glass composition that includes: SiO 2 from 65 to 75 weight percent, Na 2 O from 10 to 20 weight percent, CaO from 5 to 15 weight percent, MgO from 0 to 5 weight percent, Al 2 O 3 from 0 to 5 weight percent, K 2 O from 0 to 5 weight percent, and BaO from 0 to 1 weight percent, and a colorant and property modifying portion comprising: total iron up to 0.02 weight percent, CeO 2 from 0.05 to 1.5 weight percent, CoO up to 50 PPM, Se up to 15 PPM, Cr 2 O 3 up to 500 PPM, CuO up to 0.5 weight percent, V 2 O 5 up to 0.3 weight percent, TiO 2 up to 1 weight percent, NiO up to 200 PPM, Er 2 O 3 up to 3 weight percent, MnO 2 up to 0.6 weight percent, and Nd 2 O 3 up to 2 weight percent, wherein the glass composition has a redox ratio up to 0.55 and wherein the glass sheet exhibits an Lta
  • the present invention is a method of making a glass composition
  • a method of making a glass composition comprising: processing batch materials to form a glass composition comprising: SiO 2 from 65 to 75 weight percent, Na 2 O from 10 to 20 weight percent, CaO from 5 to 15 weight percent, MgO from 0 to 5 weight percent, Al 2 O 3 from 0 to 5 weight percent, K 2 O from 0 to 5 weight percent, and BaO from 0 to 1 weight percent, and a colorant and property modifying portion comprising: total iron up to 0.02 weight percent, CeO 2 from 0.05 weight percent to 1.5 weight percent, CoO up .
  • the glass composition has a redox ratio up to 0.55.
  • the glass composition of the present invention comprises a base glass portion and colorants and materials capable of modifying the performance properties of the glass. Both colorants and materials capable of modifying the solar control properties of the glass are referred to herein as "colorants and property modifying materials".
  • the base glass portion includes the components in the amounts shown in Table 1 below. Table 1.
  • Base Glass Portion Component Concentration in the Glass Composition [Weight Percent based on the Total Weight of the Glass Composition] SiO 2 65-75% Na 2 O 10-20% CaO 5-15% MgO 0-5% Al 2 O 3 0-5% K 2 O 0-5% BaO 0-1%
  • the described base glass portion is referred to in the art as a "soda-lime-silica" glass composition.
  • various colorants and materials capable of modifying the solar performance properties of the glass are added to the base glass composition.
  • the colorants and property modifying materials included in the glass composition of the invention include: iron oxides (both ferric oxide (Fe 2 O 3 ) and ferrous oxide (FeO)) and cerium oxide (CeO 2 ).
  • iron can be present in the glass composition as both ferric oxide (Fe 2 O 3 ) and ferrous oxide (FeO).
  • Fe 2 O 3 is a strong absorber of ultraviolet radiation and is a yellow colorant.
  • FeO is a strong absorber of infrared radiation and is a blue colorant.
  • total iron present in the glass composition of the invention is expressed in terms of the weight percentage of "Fe 2 O 3 " present in the glass composition as is standard practice in the industry. This does not imply that all of the iron present in the glass composition is in the form of Fe 2 O 3 . According to the present invention, the total iron in the glass composition of the present invention ranges up to and including 0.02 weight percent based on the total weight of the glass composition, for example, from 0.005 to 0.02 weight percent.
  • the amount of iron present in the ferrous state in the glass composition of the present invention is expressed in terms of the weight percentage of "FeO" present in the glass composition as is standard practice in the industry. Although the amount of iron in the ferrous state is expressed as FeO, the entire amount in the ferrous state may not actually be present in the glass as FeO.
  • the glass composition of the present invention has a certain "redox ratio".
  • the "redox ratio” is the amount of iron in the ferrous state (expressed as “FeO”) divided by the amount of total iron (expressed as “Fe 2 O 3 ").
  • Glass compositions according to the present invention have a redox ratio up to 0.55, for example, from 0.05 to 0.525, or from 0.1 to 0.5.
  • the glass composition of the present invention contains CeO 2 in an amount ranging from 0.05 weight percent to 1.5 weight percent, for example, from 0.50 to 1.25, or from 0.75 weight percent to 1.0 weight percent, where the weight percent is based on the total weight of the glass composition.
  • CeO 2 is known in the art as a UV absorber.
  • CeO 2 is also known in the art as a powerful oxidizing agent that oxidizes iron present in the batch materials to form Fe 2 O 3 ; which is a less powerful colorant than FeO.
  • the glass composition of the present invention can include one or more of the following optional colorants and other property modifying materials which are present primarily to determine the color exhibited by the glass composition: cobalt oxide (CoO), selenium (Se), chrome oxide (Cr 2 O 3 ), copper oxide (CuO), vanadium oxide (V 2 O 5 ), titania (TiO 2 ), nickel oxide (NiO), erbium oxide (Er 2 O 3 ), manganese oxide (MnO 2 ) and neodymium oxide (Nd 2 O 3 ).
  • cobalt oxide CoO
  • Se selenium
  • Cr 2 O 3 chrome oxide
  • CuO copper oxide
  • V 2 O 5 vanadium oxide
  • TiO 2 titanium oxide
  • NiO nickel oxide
  • Er 2 O 3 erbium oxide
  • MnO 2 manganese oxide
  • Nd 2 O 3 neodymium oxide
  • the glass composition can contain CoO in an amount up to 50 PPM, for example, from 2 PPM to 35 PPM or from 5 PPM to 25 PPM.
  • CoO operates as a blue colorant and does not exhibit any appreciable infrared or ultraviolet radiation absorbing properties.
  • the glass composition can contain Se in an amount up to 15 PPM, for example, from 3 PPM to 14 PPM or from 5 PPM to 12 PPM.
  • Se is known in the art as an ultraviolet and infrared radiation absorbing colorant that imparts a pink or brown color (the exact color depends on the valence state) to soda-lime-silica glass.
  • the glass composition can contain Cr 2 O 3 in an amount up to 500 PPM, for example, from 10 PPM to 300 PPM, or from 20 PPM to 200 PPM.
  • Cr 2 O 3 is known in the art as a green colorant.
  • the glass composition can contain CuO in an amount up to 0.5 weight percent, for example, up to 0.3 weight percent, or up to 0.1 weight percent, where the weight percent is based on the total weight of the glass composition.
  • CuO is known in the art as a blue colorant.
  • the glass composition can contain V 2 O 5 in an amount up to 0.3 weight percent, for example, up to 0.2 weight percent, or up to 0.1 weight percent, where the weight percent is based on the total weight of the glass composition.
  • V 2 O 5 is known in the art as a green colorant.
  • the glass composition can contain TiO 2 in an amount up to 1 weight percent, for example, up to 0.8 weight percent, or up to 0.6 weight percent, where the weight percent is based on the total weight of the glass composition.
  • TiO 2 is known in the art as a yellow colorant and an absorber of ultraviolet radiation.
  • the glass composition can contain NiO in an amount up to 200 PPM, for example, from 5 PPM to 100 PPM, or from 10 PPM to 50 PPM.
  • NiO is known in the art as a brown colorant.
  • the glass composition can contain Er 2 O 3 in an amount up to 3 weight percent, for example, from 0.25 to 2 weight percent, or from 0.5 to 1.5 weight percent, where the weight percent is based on the total weight of the glass composition.
  • Er 2 O 3 is known in the art as a pink colorant.
  • the glass composition can contain MnO 2 in an amount up to 0.6 weight percent, for example, from 0.1 to 0.5 weight percent, or from 0.2 to 0.4 weight percent, where the weight percent is based on the total weight of the glass composition.
  • MnO 2 is known in the art as a purple colorant.
  • the glass composition can contain Nd 2 O 3 in an amount up to 2 weight percent, for example, from 0.25 to 1.5 weight percent, or from 0.5 to 1 weight percent, where the weight percent is based on the total weight of the glass composition.
  • Nd 2 O 3 is known in the art as a blue colorant.
  • At least one of Er203 and Nd203 is present in amounts indicated in claim 1.
  • Melting and refining aids such as sulfates (SO 3 ) discussed above, may be present in the glass composition of the invention.
  • the glass composition of the present invention can be produced by conventional glass making processes.
  • the glass composition can be formed from batch materials via crucible melts, a sheet drawing process, a float glass process, etc.
  • well known batch materials are mixed with other components to form the starting materials which are processed into the glass compositions of the present invention.
  • the colorants and property modifying materials are added to the batch materials in the form of nanoparticles.
  • the glass composition of the present invention is formed via a float glass process as is well known in the art.
  • Tramp materials do not contribute to the performance properties of the glass. Tramp materials include, but are not limited to, SrO and ZrO 2 ,
  • the described glass composition is formed into a glass substrate and/or laminated glass article as is well known in the art.
  • Glass substrates having various thicknesses can be formed: For example, glass substrates having a thickness of up to 24 mm can be formed.
  • a glass substrate according to the present invention exhibits an Lta of equal to or greater than 70 percent, for example, equal to or greater than 75 percent, or equal to or greater than 80 percent at a thickness of 0.223 inches (5.664 mm).
  • a glass substrate according to the present invention is used in furniture or appliances.
  • the batch materials shown in Table 2 were weighed out, mixed thoroughly and placed in a 4 inch platinum crucible in an electric resistance furnace set to a temperature of 2,600°F (1,427°C) and heated for 2 hours.
  • the glass melt was then poured into water at room temperature (referred to as "glass fritting" in the art) to produce a glass frit.
  • the glass frit was dried in an annealing oven set to a temperature of 1,100°F (593°C) for 20 minutes.
  • the glass frit was placed back into a crucible, and the crucible was placed in an oven set to a temperature of 2,600°F (1,427°C) for 2 hours.
  • the glass melt was cast on a metal table.
  • compositional information for the exemplary glass compositions made according to the present invention is shown below in Table 3.
  • the concentration of the materials in the glass composition was determined by x-ray fluorescence chemical analysis.
  • the redox ratio was calculated from the concentration of iron oxides determined to be present in the glass composition.
  • Table 3 Glass Composition Data for Examples 1-4 Ex.1 Ex. 2 Ex. 3 Ex. 4 redox 0.147 0.050 0.208 0.224 total iron [wt.%] 0.0160 0.0150 0.0140 0.0150 CoO [PPM] 2 23 Cr 2 O 3 [PPM] 37 115 7 5 CeO 2 1 [wt. %] 0.090 0.090 0.090 0.090 0.090 1 CeO 2 and Cr 2 O 3 are in the STARPHIRE® cullet.
  • Table 4 shows various performance properties of the exemplary glass substrates having a thickness of 0.223 inches (5.6642 mm).
  • the spectral properties of the Examples were measured using a Perkin Elmer Lambda 9 spectrophotometer. According to the present invention, the abovementioned performance properties are measured as described below. All solar transmittance data are calculated using air mass solar data according to ASTM am1.5g (E892T.1). All of the transmittance values are integrated over the wavelength range using the Trapezoidal Rule, as is well known in the art.
  • the visible light transmittance (Lta) represents a computed value based on measured data using C.I.E. 1931 standard illuminant "A" over the wavelength range of 380 to 770 nanometers at 10 nanometer intervals.
  • the total solar ultraviolet transmittance (TSUV) represents a computed value based on measured data over the wavelength range of 300 to 400 nanometers at 5 nanometer intervals using the SAE 1796 standard.
  • the total solar infrared transmittance represents a computed value based on measured data over the wavelength range of 800 to 2100 nanometers at 50 nanometer intervals.
  • the total solar energy transmittance represents a computed value based on measured transmittances from 300 to 2100 nanometers at 50 nanometer intervals.
  • Color is described in terms of dominant wavelength (DW) and the excitation purity (Pe) and represents computed values based on measured data using a C.I.E. 1931 standard illuminant "C” with a 2° observer.
  • non-limiting examples of the glass composition can be used to form glass substrates having a thickness of 0.223 inches (5.6642 mm) that exhibit various colors such as green and blue.
  • Glass compositions according to the present invention can also exhibit one or more of the following performance properties in glass substrates having a thickness of 0.223 inches (5.664 mm): an Lta of equal to or greater than 80%, for example, equal to or greater than 85%; a TSET of less than 91%, for example, equal to or less than 87%, a TSUV of less than 72%, for example, equal to or less than 67%; a DW ranging from 470 to 585 nm; and a Pe up to 30%.

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Description

    FIELD OF THE INVENTION
  • The present invention relates to glass compositions, particularly, glass compositions that include minimal amounts of colorants and other property modifying materials but exhibit intense colors.
    • BACKGROUND OF THE INVENTION
  • Glass substrates are used in a variety of applications such as automotive applications, architectural applications, aerospace applications, etc. Glass substrates are also used in furniture (i.e., table tops, shelving, etc.) and appliances. Depending on the end use of the glass substrate, it is desirable for the glass substrate to exhibit certain. (a) aesthetic properties, such as, but not limited to, color and (b) solar control properties, such as, but not limited to, total solar energy transmittance ("TSET"), visible light transmittance (Lta), etc.
  • The aesthetic properties and solar control properties of a glass substrate can be modified in several of different ways. A first way involves depositing a coating on the surface of a glass substrate. A second way involves changing the chemical composition (i.e., the type of materials that make up the glass composition and/or the weight percentages of the various materials in the glass composition) that make up the glass substrate. Oftentimes, colorants and/or other materials capable of modifying the solar properties of the glass composition are added to a well known base glass composition, such as a soda-lime-silica base glass composition, to provide a glass substrate capable of exhibiting unique performance properties. Although the effect of one colorant or one material capable of modifying the solar properties of the glass composition may be known (for example, it is known that adding FeO to a base glass composition increases the infrared (IR) absorption of the glass composition), it is the essence of invention to use various colorants and/or materials capable of modifying the solar properties of the glass composition, each colorant or material capable of producing a unique effect individually, to achieve a combination of properties collectively.
  • EP 1 201 615 teaches colored glasses with high transmission.
  • According to the present invention, specific materials capable of modifying the aesthetic and/or solar properties of a glass composition are added in specific amounts to a soda-lime-silica base glass composition to provide colored glass substrates. The glass substrates of the present invention can be exhibit various colors such as, but not limited to, blue, green, yellow, bronze and gray. The glass substrates of the present invention can also exhibit an Lta of equal to or greater than 80% which is generally desirable for glass substrates used in furniture and appliances.
    • SUMMARY OF THE INVENTION
  • In an embodiment, the present invention is a glass composition comprising a base glass composition comprising: SiO2 from 65 to 75 weight percent, Na2O from 10 to 20 weight percent, CaO from 5 to 15 weight percent, MgO from 0 to 5 weight percent, Al2O3 from 0 to 5 weight percent, K2O from 0 to 5 weight percent, and BaO from 0 to 1 weight percent, and a colorant and property modifying portion comprising: total iron up to 0.02 weight percent, CeO2 from 0.05 to 1.5 weight percent, CoO up to 50PPM, Se up to 15 PPM, Cr2O3 up to 500 PPM, CuO up to 0.5 weight percent, V2O5 up to 0.3 weight percent, TiO2 up to 1 weight percent, NiO up to 200 PPM, Er2O3 up to 3 weight percent, MnO2 up to 0.6 weight percent, and Nd2O3 up to 2 weight percent, wherein the glass composition has a redox ratio up to 0,55 and comprises at least one of Er2O3 from 0,25 to 2 wt % and Nd2O3 from 0,25 to 1,5 wt %.
  • In a non-limiting embodiment, the present invention is a glass sheet comprising a glass composition that includes: SiO2 from 65 to 75 weight percent, Na2O from 10 to 20 weight percent, CaO from 5 to 15 weight percent, MgO from 0 to 5 weight percent, Al2O3 from 0 to 5 weight percent, K2O from 0 to 5 weight percent, and BaO from 0 to 1 weight percent, and a colorant and property modifying portion comprising: total iron up to 0.02 weight percent, CeO2 from 0.05 to 1.5 weight percent, CoO up to 50 PPM, Se up to 15 PPM, Cr2O3 up to 500 PPM, CuO up to 0.5 weight percent, V2O5 up to 0.3 weight percent, TiO2 up to 1 weight percent, NiO up to 200 PPM, Er2O3 up to 3 weight percent, MnO2 up to 0.6 weight percent, and Nd2O3 up to 2 weight percent, wherein the glass composition has a redox ratio up to 0.55 and wherein the glass sheet exhibits an Lta of equal to or greater than 70 percent at a thickness of 0.223 inches (5.664 mm).
  • In yet another embodiment, the present invention is a method of making a glass composition comprising: processing batch materials to form a glass composition comprising: SiO2 from 65 to 75 weight percent, Na2O from 10 to 20 weight percent, CaO from 5 to 15 weight percent, MgO from 0 to 5 weight percent, Al2O3 from 0 to 5 weight percent, K2O from 0 to 5 weight percent, and BaO from 0 to 1 weight percent, and a colorant and property modifying portion comprising: total iron up to 0.02 weight percent, CeO2 from 0.05 weight percent to 1.5 weight percent, CoO up . to 50 PPM, Se up to 15 PPM, Cr2O3 up to 500 PPM, CuO up to 0.5 weight percent, V2O5 up to 0.3 weight percent, TiO2 up to 1 weight percent, NiO up to 200 PPM, Er2O3 up to 3 weight percent, MnO2 up to 0.6 weight percent, and Nd2O3 up to 2 weight percent, wherein the glass composition has a redox ratio up to 0.55.
    • DETAILED DESCRIPTION OF THE INVENTION
  • Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Moreover, all ranges disclosed herein are to be understood to encompass the beginning and ending : range values.
  • The glass composition of the present invention comprises a base glass portion and colorants and materials capable of modifying the performance properties of the glass. Both colorants and materials capable of modifying the solar control properties of the glass are referred to herein as "colorants and property modifying materials". According to the present invention, the base glass portion includes the components in the amounts shown in Table 1 below. Table 1. Base Glass Portion
    Component Concentration in the Glass Composition [Weight Percent based on the Total Weight of the Glass Composition]
    SiO2 65-75%
    Na2O 10-20%
    CaO 5-15%
    MgO 0-5%
    Al2O3 0-5%
    K2O 0-5%
    BaO 0-1%
  • The described base glass portion is referred to in the art as a "soda-lime-silica" glass composition.
  • According to me present invention, various colorants and materials capable of modifying the solar performance properties of the glass are added to the base glass composition. The colorants and property modifying materials included in the glass composition of the invention include: iron oxides (both ferric oxide (Fe2O3) and ferrous oxide (FeO)) and cerium oxide (CeO2).
  • According to the present invention, iron can be present in the glass composition as both ferric oxide (Fe2O3) and ferrous oxide (FeO). As is well known in the art, Fe2O3 is a strong absorber of ultraviolet radiation and is a yellow colorant. As is well known in the art, FeO is a strong absorber of infrared radiation and is a blue colorant.
  • The "total iron" present in the glass composition of the invention is expressed in terms of the weight percentage of "Fe2O3" present in the glass composition as is standard practice in the industry. This does not imply that all of the iron present in the glass composition is in the form of Fe2O3. According to the present invention, the total iron in the glass composition of the present invention ranges up to and including 0.02 weight percent based on the total weight of the glass composition, for example, from 0.005 to 0.02 weight percent.
  • The amount of iron present in the ferrous state in the glass composition of the present invention is expressed in terms of the weight percentage of "FeO" present in the glass composition as is standard practice in the industry. Although the amount of iron in the ferrous state is expressed as FeO, the entire amount in the ferrous state may not actually be present in the glass as FeO.
  • The glass composition of the present invention has a certain "redox ratio". As used herein, the "redox ratio" is the amount of iron in the ferrous state (expressed as "FeO") divided by the amount of total iron (expressed as "Fe2O3"). Glass compositions according to the present invention have a redox ratio up to 0.55, for example, from 0.05 to 0.525, or from 0.1 to 0.5.
  • According to the present invention, the glass composition of the present invention contains CeO2 in an amount ranging from 0.05 weight percent to 1.5 weight percent, for example, from 0.50 to 1.25, or from 0.75 weight percent to 1.0 weight percent, where the weight percent is based on the total weight of the glass composition. CeO2 is known in the art as a UV absorber.
  • CeO2 is also known in the art as a powerful oxidizing agent that oxidizes iron present in the batch materials to form Fe2O3; which is a less powerful colorant than FeO.
  • In various non-limiting embodiments, the glass composition of the present invention can include one or more of the following optional colorants and other property modifying materials which are present primarily to determine the color exhibited by the glass composition: cobalt oxide (CoO), selenium (Se), chrome oxide (Cr2O3), copper oxide (CuO), vanadium oxide (V2O5), titania (TiO2), nickel oxide (NiO), erbium oxide (Er2O3), manganese oxide (MnO2) and neodymium oxide (Nd2O3).
  • According to the present invention, the glass composition can contain CoO in an amount up to 50 PPM, for example, from 2 PPM to 35 PPM or from 5 PPM to 25 PPM. CoO operates as a blue colorant and does not exhibit any appreciable infrared or ultraviolet radiation absorbing properties.
  • According to the present invention, the glass composition can contain Se in an amount up to 15 PPM, for example, from 3 PPM to 14 PPM or from 5 PPM to 12 PPM. Se is known in the art as an ultraviolet and infrared radiation absorbing colorant that imparts a pink or brown color (the exact color depends on the valence state) to soda-lime-silica glass.
  • According to the present invention, the glass composition can contain Cr2O3 in an amount up to 500 PPM, for example, from 10 PPM to 300 PPM, or from 20 PPM to 200 PPM. Cr2O3 is known in the art as a green colorant.
  • According to the present invention, the glass composition can contain CuO in an amount up to 0.5 weight percent, for example, up to 0.3 weight percent, or up to 0.1 weight percent, where the weight percent is based on the total weight of the glass composition. CuO is known in the art as a blue colorant.
  • According to the present invention, the glass composition can contain V2O5 in an amount up to 0.3 weight percent, for example, up to 0.2 weight percent, or up to 0.1 weight percent, where the weight percent is based on the total weight of the glass composition. V2O5 is known in the art as a green colorant.
  • According to the present invention, the glass composition can contain TiO2 in an amount up to 1 weight percent, for example, up to 0.8 weight percent, or up to 0.6 weight percent, where the weight percent is based on the total weight of the glass composition. TiO2 is known in the art as a yellow colorant and an absorber of ultraviolet radiation.
  • According to the present invention, the glass composition can contain NiO in an amount up to 200 PPM, for example, from 5 PPM to 100 PPM, or from 10 PPM to 50 PPM. NiO is known in the art as a brown colorant.
  • According to the present invention, the glass composition can contain Er2O3 in an amount up to 3 weight percent, for example, from 0.25 to 2 weight percent, or from 0.5 to 1.5 weight percent, where the weight percent is based on the total weight of the glass composition. Er2O3 is known in the art as a pink colorant.
  • According to the present invention, the glass composition can contain MnO2 in an amount up to 0.6 weight percent, for example, from 0.1 to 0.5 weight percent, or from 0.2 to 0.4 weight percent, where the weight percent is based on the total weight of the glass composition. MnO2 is known in the art as a purple colorant.
  • According to the present invention, the glass composition can contain Nd2O3 in an amount up to 2 weight percent, for example, from 0.25 to 1.5 weight percent, or from 0.5 to 1 weight percent, where the weight percent is based on the total weight of the glass composition. Nd2O3 is known in the art as a blue colorant. At least one of Er203 and Nd203 is present in amounts indicated in claim 1.
  • Melting and refining aids such as sulfates (SO3) discussed above, may be present in the glass composition of the invention.
  • The glass composition of the present invention can be produced by conventional glass making processes. For example, the glass composition can be formed from batch materials via crucible melts, a sheet drawing process, a float glass process, etc. Typically, well known batch materials are mixed with other components to form the starting materials which are processed into the glass compositions of the present invention.
  • In a non-limiting embodiment of the present invention, the colorants and property modifying materials are added to the batch materials in the form of nanoparticles.
  • In another non-limiting embodiment, the glass composition of the present invention is formed via a float glass process as is well known in the art.
  • As a result of the raw materials and/or equipment used to produce the glass composition of the present invention, certain impurities can be present in the final glass composition. Such materials are present in the glass composition in minor amounts and are referred to herein as "tramp materials". Tramp materials do not contribute to the performance properties of the glass. Tramp materials include, but are not limited to, SrO and ZrO2,
  • In a non-limiting embodiment of the invention, the described glass composition is formed into a glass substrate and/or laminated glass article as is well known in the art. Glass substrates having various thicknesses can be formed: For example, glass substrates having a thickness of up to 24 mm can be formed.
  • In a non-limiting embodiment a glass substrate according to the present invention, exhibits an Lta of equal to or greater than 70 percent, for example, equal to or greater than 75 percent, or equal to or greater than 80 percent at a thickness of 0.223 inches (5.664 mm).
  • In a non-limiting embodiment of the invention, a glass substrate according to the present invention is used in furniture or appliances.
    • EXAMPLES
  • The following examples are outside the scope of the present invention. The Examples 1-4 were made in the following manner.
  • The batch materials shown in Table 2 were weighed out, mixed thoroughly and placed in a 4 inch platinum crucible in an electric resistance furnace set to a temperature of 2,600°F (1,427°C) and heated for 2 hours. The glass melt was then poured into water at room temperature (referred to as "glass fritting" in the art) to produce a glass frit. The glass frit was dried in an annealing oven set to a temperature of 1,100°F (593°C) for 20 minutes. The glass frit was placed back into a crucible, and the crucible was placed in an oven set to a temperature of 2,600°F (1,427°C) for 2 hours. The glass melt was cast on a metal table. The resulting glass sheet was placed into an annealing lehr set to a temperature of 1,125°F (607°C) for one hour. The power to the lehr was shut off, and the glass sheet was allowed to stay in the lehr for sixteen hours as it cooled down to room temperature. Examples made from the glass melts were ground and polished. Table 2. Glass Batch Materials for Examples 1-4
    Ex. 1 Ex. 2 Ex.3 Ex. 4
    STARPHIRE® Cullet1 [g] 500 500 500 500
    Cr2O3 [g] 0.0156 0.0625
    CoO [g] 0.0026 0.0104
    1STARPHIRE® cullet refers to glass that is commercially available from PPG Industries, Inc. (Pittsburgh, PA) under the name of STARPHIRE® glass, which is broken up and added to the batch materials as described above.
  • Compositional information for the exemplary glass compositions made according to the present invention is shown below in Table 3. The concentration of the materials in the glass composition was determined by x-ray fluorescence chemical analysis. The redox ratio was calculated from the concentration of iron oxides determined to be present in the glass composition. Table 3. Glass Composition Data for Examples 1-4
    Ex.1 Ex. 2 Ex. 3 Ex. 4
    redox 0.147 0.050 0.208 0.224
    total iron [wt.%] 0.0160 0.0150 0.0140 0.0150
    CoO [PPM] 2 23
    Cr2O3 [PPM] 37 115 7 5
    CeO2 1[wt. %] 0.090 0.090 0.090 0.090
    1CeO2 and Cr2O3 are in the STARPHIRE® cullet.
  • Table 4 shows various performance properties of the exemplary glass substrates having a thickness of 0.223 inches (5.6642 mm). The spectral properties of the Examples were measured using a Perkin Elmer Lambda 9 spectrophotometer. According to the present invention, the abovementioned performance properties are measured as described below. All solar transmittance data are calculated using air mass solar data according to ASTM am1.5g (E892T.1). All of the transmittance values are integrated over the wavelength range using the Trapezoidal Rule, as is well known in the art.
  • The visible light transmittance (Lta) represents a computed value based on measured data using C.I.E. 1931 standard illuminant "A" over the wavelength range of 380 to 770 nanometers at 10 nanometer intervals.
  • The total solar ultraviolet transmittance (TSUV) represents a computed value based on measured data over the wavelength range of 300 to 400 nanometers at 5 nanometer intervals using the SAE 1796 standard.
  • The total solar infrared transmittance (TSIR) represents a computed value based on measured data over the wavelength range of 800 to 2100 nanometers at 50 nanometer intervals.
  • The total solar energy transmittance (TSET) represents a computed value based on measured transmittances from 300 to 2100 nanometers at 50 nanometer intervals.
  • Color is described in terms of dominant wavelength (DW) and the excitation purity (Pe) and represents computed values based on measured data using a C.I.E. 1931 standard illuminant "C" with a 2° observer.
  • The visible color was determined by a single observer and indicates the color visibly observed by an average person. Table 4. Performance Properties for Examples 1-4
    Ex. 1 Ex. 2 Ex. 3 Ex. 4
    Lta [%] 89.81 87.94 90.08 81.29
    TSUV [%] 70.57 69.40 70.98 70.54
    TSIR [%] 89.82 91.08 89.32 88.25
    TSET [%] 88.88 87.93 89.23 85.54
    DW [nm] 561.36 560.79 486.26 477.98
    Pe[%] 1.08 2.70 0.19 4.94
    Visible Color green green blue blue
  • Based on Table 4, non-limiting examples of the glass composition can be used to form glass substrates having a thickness of 0.223 inches (5.6642 mm) that exhibit various colors such as green and blue. Glass compositions according to the present invention can also exhibit one or more of the following performance properties in glass substrates having a thickness of 0.223 inches (5.664 mm): an Lta of equal to or greater than 80%, for example, equal to or greater than 85%; a TSET of less than 91%, for example, equal to or less than 87%, a TSUV of less than 72%, for example, equal to or less than 67%; a DW ranging from 470 to 585 nm; and a Pe up to 30%.
  • It will be readily appreciated by those skilled in the art that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. Such modifications are to be considered as included within the scope of the invention. Accordingly, the particular embodiments described in detail hereinabove are illustrative only and are not limiting as to the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalents thereof.

Claims (14)

  1. A glass composition comprising a base glass composition comprising: SiO2 65 to 75 weight percent, Na2O 10 to 20 weight percent, CaO 5 to 15 weight percent, MgO 0 to 5 weight percent, Al2O3 0 to 5 weight percent, K2O 0 to 5 weight percent, and BaO 0 to 1 weight percent,
    and a colorant and property modifying portion comprising: total iron up to 0.02 weight percent, CeO2 0.05 to 1.5 weight percent, CoO 0 to 50 PPM, Se 0 to 15 PPM, Cr2O3 0 to 500 PPM, CuO 0 to 0.5 weight percent, V2O5 0 to 0.3 weight percent, TiO2 0 to 1 weight percent, NiO 0 to 200 PPM, Er2O3 0 to 3 weight percent, MnO2 0 to 0.6 weight percent, and Nd2O3 0 to 2 weight percent,
    wherein the glass composition has a redox ratio up to 0.55, characterized in that at least one of the following materials is present in the recited amount: Er2O3 from 0.25 to 2 weight percent and Nd2O3 from 0.25 to 1.5 weight percent.
  2. The glass composition according to claim 1, wherein the redox ratio ranges from 0.05 to 0.525.
  3. The glass composition according to claim 1, wherein the CeO2 ranges from 0.75 weight percent to 1.0 weight percent.
  4. The glass composition according to claim 1, wherein the redox ratio ranges from 0.1 to 0.5.
  5. The glass composition according to claim 1, wherein at least one of the following materials is present in the recited amount: CoO from 2 to 35 PPM, Se from 3 to 14 PPM, Cr2O3 from 10 to 300 PPM, CuO up to 0.3 weight percent, V2O5 up to 0.2 weight percent, TiO2 from 0.15 to 0.8 weight percent, NiO from 5 to 100 PPM, and MnO2 from 0.1 to 0.5 weight percent.
  6. The glass composition according to claim 5, wherein at least one of the following materials is present in the recited amount: CoO from 5 to 25 PPM, Se from 5 to 12 PPM, Cr2O3 from 20 to 200 PPM, CuO up to 0.1 weight percent, V2O5 up to 0.1 weight percent, TiO2 from 0.2 to 0.6 weight percent, NiO from 10 to 50 PPM, Er2O3 from 0.5 to 1.5 weight percent, MnO2 from 0.2 to 0.4 weight percent, and Nd2O3 from 0.5 to 1 weight percent.
  7. A glass sheet made from the composition according to claim 1.
  8. A glass sheet according to claim 7 that exhibits an Lta greater than or equal to 70% at a thickness of 0.223 inches (5.664 mm).
  9. A glass sheet according to claim 8 that exhibits an Lta greater than or equal to 85% at a thickness of 0.223 inches (5.664 mm).
  10. The glass sheet according to claim 8, wherein at least one of the following materials is present in the glass composition in the recited amount: CoO from 2 to 35 PPM, Se from 3 to 14 PPM, Cr2O3 from 10 to 300 PPM, CuO up to 0.3 weight percent, V2O5 up to 0.2 weight percent, TiO2 from 0.15 to 0.8 weight percent, NiO from 5 to 100 PPM, and MnO2 from 0.1 to 0.5 weight percent.
  11. A method of making a glass composition comprising: processing batch materials to form a glass composition comprising: SiO2 65 to 75 weight percent, Na2O 10 to 20 weight percent, CaO 5 to 15 weight percent, MgO 0 to 5 weight percent, Al2O3 0 to 5 weight percent, K2O 0 to 5 weight percent, and BaO 0 to 1 weight percent,
    and a colorant and property modifying portion comprising: total iron up to 0.02 weight percent, CeO2  0.05 weight percent to 1.5 weight percent, CoO  0 to 50 PPM, Se  0 to 15 PPM, Cr2O3  0 to 500 PPM, CuO  0 to 0.5 weight percent, V2O5  0 to 0.3 weight percent, TiO2  0 to 1 weight percent, NiO  0 to 200 PPM, Er2O3  0 to 3 weight percent, MnO2  0 to 0.6 weight percent, and Nd2O3  0 to 2 weight percent,
    wherein the glass composition has a redox ratio up to 0.55, characterized in that at least one of the following materials is present in the recited amount:
    Er2O3 from 0.25 to 2 weight percent and Nd2O3 from 0.25 to 1.5 weight percent.
  12. The method according to claim 11, wherein at least one of the following materials is present in glass composition in the recited amount: CoO from 2 to 35 PPM, Se from 3 to 14 PPM, Cr2O3 from 10 to 300 PPM, CuO up to 0.3 weight percent, V2O5 up to 0.2 weight percent, TiO2 from 0.15 to 0.8 weight percent, NiO from 5 to 100 PPM, and MnO2 from 0.1 to 0.5 weight percent.
  13. The method according to claim 12, wherein at least one of the following materials is present in the glass composition in the recited amount: CoO from 5 to 25 PPM, Se from 5 to 12 PPM, Cr2O3 from 20 to 200 PPM, CuO up to 0.1 weight percent, V2O5 up to 0.1 weight percent, TiO2 from 0.2 to 0.6 weight percent, NiO from 10 to 50 PPM, Er2O3 from 0.5 to 1.5 weight percent, MnO2 from 0.2 to 0.4 weight percent, and Nd2O3 from 0.5 to 1 weight percent.
  14. The method according to claim 13, further comprising forming the glass composition into a flat sheet.
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US20070161492A1 (en) 2007-07-12
PL1984306T3 (en) 2019-09-30
CN101370743A (en) 2009-02-18
WO2007087125A1 (en) 2007-08-02
CN101370743B (en) 2012-01-25
US7825051B2 (en) 2010-11-02
HUE045085T2 (en) 2019-12-30
ES2728796T3 (en) 2019-10-28
CA2636754A1 (en) 2007-08-02
CA2636754C (en) 2012-03-20

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